Abstract
Mn K-edge X-ray absorption measurements were carried out on an amorphous manganese oxi-iodide (Li0.60Na0.16MnO2.33I0.05) as cathode material in plastic lithium batteries. X-ray absorption spectroscopy experiments were performed in situ for every lithium intercalation increment Dx≈0.10 per formula unit along a discharge with 0<x<0.67. The X-ray absorption near edge structure (XANES) spectra demonstrate a smooth decrease of Mn valence with in-situ reduction, confirmed by a monotonous increase in Mn-O distance from extended X-ray absorption fine structure (EXAFS). The first-shell octahedral coordination of manganese is hardly affected by lithium insertion, while the evolution of the Mn-Mn coordinence shows a trend towards the formation of MnOn polyhedra chains on deep discharge. The material discharged to an average manganese valence 3.25+ showed negligible static Jahn-Teller effect. Together with the inherent flexibility of disordered structures towards intercalation and bond length changes, this is probably a major cause of the stability of this oxi-iodide on cycling in lithium batteries.